Enhanced electrochemical biosensor and supercapacitor with 3D porous architectured graphene via salt impregnated inkjet maskless lithography

Abstract

Advances in solution-phase graphene patterning has provided a facile route for rapid, low-cost and scalable manufacturing of electrochemical devices, even on flexible substrates. While graphene possesses advantageous electrochemical properties of high surface area and fast heterogenous charge transport, these properties are attributed to the edge planes and defect sites, not the basal plane. Herein, we demonstrate enhancement of the electroactive nature of patterned solution-phase graphene by increasing the porosity and edge planes through the construction of a multidimensional architecture via salt impregnated inkjet maskless lithography (SIIML) and CO₂ laser annealing. Various sized macroscale pores (<25 to ∼250 μm) are patterned directly in the graphene surface by incorporating porogens (i.e., salt crystals) in the graphene ink which act as hard templates for pore formation and are later dissolved in water. Subsequently, microsized pores (∼100 nm to 2 μm in width) with edge plane defects are etched in the graphene lattice structure by laser annealing with a CO₂ laser, simultaneously improving electrical conductivity by nearly three orders of magnitude (sheet resistance decreases from >10 000 to ∼50 Ω sq⁻¹). We demonstrate that this multidimensional porous graphene fabrication method can improve electrochemical device performance through design and manufacture of an electrochemical organophosphate biosensor that uses the enzyme acetylcholinesterase for detection. This pesticide biosensor exhibits enhanced sensitivity to acetylthiocholine compared to graphene without macropores (28.3 μA nM⁻¹ to 13.3 μA nM⁻¹) and when inhibited by organophosphate pesticides (paraoxon) has a wide linear range (10 nM to 500 nM), low limit of detection (0.6 nM), and high sensitivity (12.4 nA nM⁻¹). Moreover, this fabrication method is capable of patterning complex geometries [i.e. interdigitated electrodes (IDEs)] even on flexible surfaces as demonstrated by an IDE supercapacitor made of SIIML graphene on a heat sensitive polymer substrate. The supercapacitor demonstrates a high energy density of 0.25 mW h cm⁻³ at a power density of 0.3 W cm⁻³. These electrochemical devices demonstrate the benefit of using SIIML and CO₂ laser annealing for patterning graphene electrodes with a multidimensional porous surface even on flexible substrates and is therefore a platform technology which could be applied to a variety of different biosensors and other electrochemical devices.